EP0237483B1 - Microbicides - Google Patents

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Publication number
EP0237483B1
EP0237483B1 EP87810116A EP87810116A EP0237483B1 EP 0237483 B1 EP0237483 B1 EP 0237483B1 EP 87810116 A EP87810116 A EP 87810116A EP 87810116 A EP87810116 A EP 87810116A EP 0237483 B1 EP0237483 B1 EP 0237483B1
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EP
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Prior art keywords
cis
propiconazol
formula
active ingredient
mainly
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Expired
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EP87810116A
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German (de)
French (fr)
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EP0237483A1 (en
Inventor
Reinhard Dr. Janicke
Robert Dr. Nyfeler
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Novartis AG
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Ciba Geigy AG
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Priority to AT87810116T priority Critical patent/ATE44641T1/en
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4

Definitions

  • the present invention relates to fungicidal mixtures with a synergistically increased activity against fungi and to methods of using such mixtures.
  • the agents according to the present invention are based on two active ingredients, both of which have become known as ergosterol synthesis inhibitors.
  • Component I is the active ingredient propiconazole, 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazot of the formula or one of its salts.
  • the active ingredient is described in GB-1,522,657.
  • Component II is the active ingredient fenpropimorph, 4- [3- (4-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethylmorpholine of the formula or one of its salts.
  • the active ingredient is described in DE-OS 27 52 096, which corresponds to GB-PS 1,584,290.
  • Propiconazole, component I can exist in four stereoisomeric forms which have different fungicidal activity.
  • the two cis isomers are preferred, i. H. those enantiomers in which the triazolylmethyl group and the propyl group are on the same side of the dioxolane ring.
  • Fenpropimorph, the cis component 11 occurs in two enantiomeric forms, of which the (-) - enantiomer, which has the S configuration, is preferred as the active partner.
  • the invention includes mixtures of pure isomers I and II, in particular mixtures of a cis enantiomer of propiconazole with the (-) cis enantiomer of fenpropimorph.
  • the invention also includes agents and control methods in which the active ingredient component I, propiconazole, is predominantly in the form of the two cis enantiomers.
  • the invention particularly includes agents and corresponding control methods in which the active ingredient component propiconazole is predominantly present as one of the cis enantiomers and fenpropimorph predominantly as the (-) cis enantiomer which has the S configuration.
  • the acids which can be used to prepare salts of the formula I or II include: hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, and sulfuric acid, phosphoric acid, nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid , Thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalenic acid disodium.
  • hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid
  • sulfuric acid
  • salts also includes metal complexes of the two basic components I and II. These complexes can optionally affect only one component or both components independently. It is also possible to produce metal complexes which combine the two active compounds 1 and II to form a mixed complex.
  • Metal complexes consist of the underlying organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the second main group such as calcium and magnesium and the third and fourth main groups such as aluminum, tin or lead and the first to eighth subgroups such as chromium, manganese, iron, cobalt, nickel, copper, zinc etc. The subgroup elements of the fourth period are preferred.
  • the metals can be present in the various valences that come with them.
  • the metal complexes can occur single or multi-core, i. H. they can contain one or more organic moieties as ligands, such as in the aforementioned mixed complexes of propiconazole and fenpropimorph.
  • ergosterol biosynthesis inhibitors have been increasingly on the Market has come, ie preparations whose fungicidal action is based on preventing the biosynthesis of ergosterol occurring in the cell membrane of fungi.
  • DMI 14-C demethylation inhibitor
  • the present invention therefore represents a very substantial enrichment of the technology.
  • the present invention also relates to a method for combating fungi, which is characterized by treating an area infected or endangered by fungi in any order or simultaneously with a) the active ingredient propiconazole of the formula I or one of its salts and with b) the active ingredient fenpropimorph of the formula II or one of its salts, the salts also being able to be chosen such that both active ingredients are bound to an acid residue or, in the case of a metal complex, to a central metal cation.
  • the active compound mixtures I + II according to the invention have very advantageous curative, preventive and systemic fungicidal properties for protecting crop plants.
  • the present active ingredient mixtures on plants or on parts of plants (fruits, flowers, foliage, stems, tubers, roots) of different useful cultures can be used to contain or destroy the microorganisms which occur, with plant parts which are growing later being spared by such microorganisms. This applies in particular to microorganisms that have developed reduced sensitivity to fungicides from the triazole class.
  • the active substance mixtures are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidiomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Altemaria and especially Pyricularia).
  • the active ingredient mixtures have a systemic effect.
  • the active substance mixtures according to the invention are notable for particularly good plant tolerance and for their environmental friendliness.
  • Target cultures for the areas of indication disclosed herein include z. B. the following types of plants: cereals: (wheat, barley, rye, oats, rice, sorghum and relatives); Beets: (sugar and fodder beets); Pome, stone and berry fruit: (apples, pears, plums, peaches, almonds, cherries, strawberries, strawberries and blackberries); Legumes: (beans, lentils, peas, soy); Oil cultures: (rapeseed, mustard, poppy seeds, olives, sunflowers, coconut, castor bean, cocoa, peanuts); Cucumber Family: (Pumpkin, Cucumber, Melon); Fiber plants: (cotton, flax, hemp, jute); Citrus fruits: (oranges, lemons, grapefruit, mandarins); Vegetables: (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel plants: (avocado, cinnamonum, camphor) or
  • the active ingredient mixtures of the formulas I and 11 are usually used in the form of compositions.
  • the active ingredients of the formula I and those of the formula II can be applied simultaneously to the area or plant to be treated, together with any other carriers, surfactants or other application-promoting additives customary in formulation technology.
  • Suitable carriers and additives can be solid or liquid and correspond to the substances useful in formulation technology, such as. B. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
  • a preferred method of applying a mixture of active ingredients which contains at least one of each of these active ingredients I and 11 is the application to the aerial parts of the plants, in particular the foliage (leaf application).
  • the number of applications and the application rate depend on the biological and climatic living conditions for the pathogen.
  • the active ingredients can also get into the plant through the roots through the roots (systemic effect) by soaking the location of the plant with a liquid preparation or introducing the substances in solid form into the soil, e.g. B. in the form of granules (floor application).
  • the compounds of the formulas I and II can also be applied to seeds (coating) by either soaking the grains in succession in a liquid preparation of an active ingredient or coating them with an already combined preparation.
  • other types of application to plants are possible in special cases, e.g. B. the targeted treatment of the buds or the fruit heads.
  • the compounds of the combination are used in unchanged form or preferably together with the auxiliaries customary in formulation technology and are therefore used, for.
  • the application methods such as spraying, atomizing, dusting, scattering, brushing or pouring, are selected in the same way as the type of agent, in accordance with the intended objectives and the prevailing conditions.
  • Favorable application rates are generally 50 g to 2 kg ai / ha, in particular 100 g to 600 g ai / ha.
  • the formulations are prepared in a known manner, e.g. B. by intimately mixing and / or grinding the active ingredients with extenders, such as. B. with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • extenders such as. B. with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • Aromatic hydrocarbons preferably fractions C 8 to C, 2 , such as.
  • solid carriers e.g. B. for dusts and dispersible powders, natural rock flours are usually used, such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silica or highly disperse absorbent polymers can also be added.
  • adsorptive granulate carriers come porous types such.
  • pumice broken brick, sepiolite or bentonite, as non-sorptive support materials such.
  • B. calcite or sand in question.
  • a large number of pregranulated materials of inorganic or organic nature such as, in particular, dolomite or comminuted plant residues can be used.
  • application-promoting additives that can lead to a reduction in the application rate are also natural (animal or vegetable) or synthetic phospholipids from the series of kephalins and lecithins, such as. B. phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, lysolecithin, plasmalogens or cardiolipin, which can be obtained, for example, from animal or plant cells, in particular from the brain, heart, liver, egg yolk or soybeans.
  • Usable commercial mixtures are e.g. B. phosphatidylchlorine mixtures.
  • Synthetic phospholipids are e.g. B. dioctanoylphosphatidylcholine and dipalmitoylphosphatidylcholine.
  • suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties.
  • surfactants are also to be understood as mixtures of surfactants.
  • the active ingredient is mixed well with the additives and ground well in a suitable mill.
  • Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
  • Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.
  • the active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
  • the finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
  • Fungicides always have a synergistic effect if the fungicidal activity of the active ingredient combination is greater than the sum of the effects of the individually applied active ingredients.
  • the individual active ingredient or the fungicide mixture is applied as an aqueous suspension with a spray bar under field conditions. After the application, the change in the infestation on the leaf surface present in the case of inoculation (evaluation of the primary infestation) is determined at regular intervals.
  • tests 9 to 16 have a synergistically increased fungicidal action with very different mixing ratios.

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  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
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Abstract

1. A composition for controlling phytopathogenic fungi and for preventing fungus attack based on a mixture of two plant fungicides in admixture with a suitable carrier and/or extender, wherein the composition contains as component l the active ingredient 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylme- thyl]-1H- 1,2,4-triazol (= propiconazol) of formula l see diagramm : EP0237483,P7,F1 or a salt thereof and as component ll the active ingredient 4-[3-(4-tert. butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine (= fenpropimorph) of formula ll see diagramm : EP0237483,P7,F2 or a salt thereof in an amount producing synergistic fungicidal activity.

Description

Die vorliegende Erfindung betrifft fungizide Gemische mit synergistisch gesteigerter Wirkung gegen Pilze und Verfahren zur Anwendung solcher Gemische.The present invention relates to fungicidal mixtures with a synergistically increased activity against fungi and to methods of using such mixtures.

Die Mittel gemäss vorliegender Erfindung basieren auf zwei Wirkstoffen, die beide als Ergosterin-Synthesehemmer bekannt geworden sind.The agents according to the present invention are based on two active ingredients, both of which have become known as ergosterol synthesis inhibitors.

Die Komponente I ist der Wirkstoff Propiconazol, 1-[2-(2,4-Dichlorphenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazot der Formel

Figure imgb0001
oder eines seiner Salze. Der Wirkstoff wird in der GB-1,522,657 beschrieben.Component I is the active ingredient propiconazole, 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazot of the formula
Figure imgb0001
 or one of its salts. The active ingredient is described in GB-1,522,657.

Die Komponente II ist der Wirkstoff Fenpropimorph, 4-[3-(4-tert. Butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholin der Formel

Figure imgb0002
oder eines seiner Salze. Beschrieben wird der Wirkstoff in der DE-OS 27 52 096, die der GB-PS 1,584,290 entspricht.Component II is the active ingredient fenpropimorph, 4- [3- (4-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethylmorpholine of the formula
Figure imgb0002
 or one of its salts. The active ingredient is described in DE-OS 27 52 096, which corresponds to GB-PS 1,584,290.

Propiconazol, die Komponente I, kann in vier stereoisomeren Formen vorliegen, die unterschiedliche fungizide Wirkung haben. Bevorzugt sind die beiden cis-Isomeren, d. h. jene Enantiomeren, bei denen die Triazolylmethylgruppe und die Propylgruppe auf der gleichen Seite des Dioxolanringes stehen. Fenpropimorph, die cis-Komponente 11, tritt in zwei enantiomeren Formen auf, von denen das (-)-Enantiomere, das S-Konfiguration besitzt, als Wirkungspartner bevorzugt ist. Die Erfindung schliesst Gemische reiner Isomeren I und II mit ein, insbesondere Gemische aus einem cis-Enantiomeren des Propiconazol mit dem (-) cis-Enantiomeren des Fenpropimorph.Propiconazole, component I, can exist in four stereoisomeric forms which have different fungicidal activity. The two cis isomers are preferred, i. H. those enantiomers in which the triazolylmethyl group and the propyl group are on the same side of the dioxolane ring. Fenpropimorph, the cis component 11, occurs in two enantiomeric forms, of which the (-) - enantiomer, which has the S configuration, is preferred as the active partner. The invention includes mixtures of pure isomers I and II, in particular mixtures of a cis enantiomer of propiconazole with the (-) cis enantiomer of fenpropimorph.

Die Erfindung schliesst auch Mittel und Bekämpfungsverfahren ein, bei denen die Wirkstoff-Komponente I, Propiconazol, überwiegend in der Form der beiden cis-Enantiomeren vorliegt.The invention also includes agents and control methods in which the active ingredient component I, propiconazole, is predominantly in the form of the two cis enantiomers.

Die Erfindung schliesst insbesondere Mittel und entsprechende Bekämpfungsverfahren ein, bei denen die Wirkstoff-Komponente Propiconazol überwiegend als eines der cis-Enantiomeren und Fenpropimorph überwiegend als das (-) cis-Enantiomere vorliegt, welches S-Konfiguration besitzt.The invention particularly includes agents and corresponding control methods in which the active ingredient component propiconazole is predominantly present as one of the cis enantiomers and fenpropimorph predominantly as the (-) cis enantiomer which has the S configuration.

Unter den Säuren, die zur Herstellung von Salzen der Formel I oder II verwendet werden können, sind zu nennen : Halogenwasserstoffsäure wie Fluorwasserstoffsäure, Chlorwasserstoffsäure, Bromwasserstoffsäure oder Jodwasserstoffsäure sowie Schwefelsäure, Phosphorsäure, Salpetersäure und organische Säuren wie Essigsäure, Trifluoressigsäure, Trichloressigsäure, Propionsäure, Glycolsäure, Thiocyansäure, Milchsäure, Bernsteinsäure, Zitronensäure, Benzoesäure, Zimtsäure, Oxalsäure, Ameisensäure, Benzolsulfonsäure, p-Toluolsulfonsäure, Methansulfonsäure, Salicylsäure, p-Aminosalicylsäure, 2-Phenoxybenzoesäure, 2-Acetoxybenzoesäure oder 1,2-Naphthalin-disulfonsäure.The acids which can be used to prepare salts of the formula I or II include: hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, and sulfuric acid, phosphoric acid, nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid , Thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid or 1,2-naphthalenic acid disodium.

Der Begriff Salze schliesst auch Metallkomplexe der beiden basischen Komponenten I und II ein. Diese Komplexe können wahlweise nur eine Komponente oder auch beide Komponenten unabhängig betreffen. Es lassen sich auch Metallkomplexe herstellen, die beide Wirkstoffe 1 und II miteinander zu einem gemischten Komplex verbinden.The term salts also includes metal complexes of the two basic components I and II. These complexes can optionally affect only one component or both components independently. It is also possible to produce metal complexes which combine the two active compounds 1 and II to form a mixed complex.

Metallkomplexe bestehen aus dem zugrundeliegenden organischen Molekül und einem anorganischen oder organischen Metallsalz, beispielsweise den Halogeniden, Nitraten, Sulfaten, Phosphaten, Acetaten, Trifluoracetaten, Trichloracetaten, Propionaten, Tartraten, Sulfonaten, Salicylaten, Benzoaten usw. der Elemente der zweiten Hauptgruppe wie Calcium und Magnesium und der dritten und vierten Hauptgruppe wie Aluminium, Zinn oder Blei sowie der ersten bis achten Nebengruppe wie Chrom, Mangan, Eisen, Kobalt, Nickel, Kupfer, Zink usw. Bevorzugt sind die Nebengruppen-Elemente der 4. Periode. Die Metalle können dabei in den verschiedenen ihnen zukommenden Wertigkeiten vorliegen. Die Metallkomplexe können ein- oder mehrkemig auftreten, d. h. sie können ein oder mehrere organische Molekülanteile als Liganden enthalten, wie etwa bei den vorerwähnten Mischkomplexen aus Propiconazol und Fenpropimorph.Metal complexes consist of the underlying organic molecule and an inorganic or organic metal salt, for example the halides, nitrates, sulfates, phosphates, acetates, trifluoroacetates, trichloroacetates, propionates, tartrates, sulfonates, salicylates, benzoates etc. of the elements of the second main group such as calcium and magnesium and the third and fourth main groups such as aluminum, tin or lead and the first to eighth subgroups such as chromium, manganese, iron, cobalt, nickel, copper, zinc etc. The subgroup elements of the fourth period are preferred. The metals can be present in the various valences that come with them. The metal complexes can occur single or multi-core, i. H. they can contain one or more organic moieties as ligands, such as in the aforementioned mixed complexes of propiconazole and fenpropimorph.

In der Praxis setzt man vorteilhaft die reinen Wirkstoffe 1 und II ein, denen man auch weitere agrarchemische Aktivsubstanzen wie Insektizide, Akarizide, Nematizide, Herbizide, Wuchsregulatoren und Düngemittel, insbesondere aber weitere Mikrobizide, zufügen kann.In practice, it is advantageous to use pure active ingredients 1 and II, to which other agrochemical active ingredients such as insecticides, acaricides, nematicides, herbicides, growth regulators and fertilizers, but in particular other microbicides, can be added.

In den letzten Jahren sind sogenannte Ergosterin-Biosynthese-Hemmer in verstärktem Masse auf den Markt gekommen, d. h. Präparate, deren Fungizid-Wirkung darauf beruht, die Biosynthese des in der Zellmembran von Pilzen vorkommenden Ergosterins zu hindern. Fungizide, die im Molekül einen 1 H-1,2,4-Triazolrest enthalten, wirken in der Regel bei diesem Vorgang als 14-C Demethylierungshemmer ( = DMI). Der jahrelange Einsatz von Präparaten auf Triazol-Basis hat allerdings stellenweise schon zum Auftreten von Pilzstämmen mit nachweislich reduzierter Sensitivität geführt.In recent years, so-called ergosterol biosynthesis inhibitors have been increasingly on the Market has come, ie preparations whose fungicidal action is based on preventing the biosynthesis of ergosterol occurring in the cell membrane of fungi. Fungicides that contain a 1 H-1,2,4-triazole residue in the molecule usually act as a 14-C demethylation inhibitor (= DMI) in this process. However, the years of use of triazole-based preparations have in some cases already led to the appearance of fungal strains with demonstrably reduced sensitivity.

Es hat sich nun überraschenderweise gezeigt, dass Mischungen von Propiconazol mit Fenpropimorph in ihrer fungiziden Wirkung nicht nur additive Wirkung, sondern deutlich synergistisch gesteigerte Wirkung entfalten. Indessen ist für die Anwendungspraxis ein weiterer Faktor von ausserordentlicher Wichtigkeit, nämlich die in keiner Weise vorhersehbare Tatsache, dass die synergistisch gesteigerte Wirkung auch bei Pilz-Isolaten beobachtet wird, die eine reduzierte Sensitivität auf Triazol-Fungizide erworben haben.It has now surprisingly been found that mixtures of propiconazole with fenpropimorph not only have an additive action in their fungicidal action, but also a significantly synergistically increased action. However, a further factor of extraordinary importance for practical use, namely the fact that it is in no way foreseeable that the synergistically increased effect is also observed in fungal isolates which have acquired a reduced sensitivity to triazole fungicides.

Die vorliegende Erfindung stellt daher eine ganz wesentliche Bereicherung der Technik dar.The present invention therefore represents a very substantial enrichment of the technology.

Gegenstand der vorliegenden Erfindung ist neben dem Zweikomponenten-Gemisch auch ein Verfahren zur Bekämpfung von Pilzen, das gekennzeichnet ist durch Behandlung einer durch Pilze befallenen oder gefährdeten Stelle in beliebiger Reihenfolge oder gleichzeitig mit a) dem Wirkstoff Propiconazol der Formel I oder einem seiner Salze und mit b) dem Wirkstoff Fenpropimorph der Formel II oder einem seiner Salze, wobei die Salze auch so gewählt sein können, dass beide Wirkstoffe an einen Säurerest oder, im Falle eines Metallkomplexes, an ein zentrales Metall-Kation gebunden sind.In addition to the two-component mixture, the present invention also relates to a method for combating fungi, which is characterized by treating an area infected or endangered by fungi in any order or simultaneously with a) the active ingredient propiconazole of the formula I or one of its salts and with b) the active ingredient fenpropimorph of the formula II or one of its salts, the salts also being able to be chosen such that both active ingredients are bound to an acid residue or, in the case of a metal complex, to a central metal cation.

Günstige Mischungsverhältnisse der beiden Wirkstoffe sind I : II =10 :1 1 bis 1 : 20, bevorzugt I : II = 5 : bis 1 : 5. In vielen Fällen sind Mischungen vorteilhaft, bei denen das Mischungsverhältnis der reinen Aktivsubstanzen I : 11 = 1 : bis 1 : 5 beträgt, z. B. 2 : 5.Favorable mixing ratios of the two active ingredients are I: II = 10: 1 1 to 1:20, preferably I: II = 5: to 1: 5. In many cases, mixtures are advantageous in which the mixing ratio of the pure active substances I: 11 = 1 : up to 1: 5, e.g. B. 2: 5.

Die erfindungsgemässen Wirkstoffmischungen I + II besitzen sehr vorteilhafte kurative, präventive und systemische Fungizid-Eigenschaften zum Schutz von Kulturpflanzen. Mit den vorliegenden Wirkstoffmischungen können an Pflanzen oder an Pflanzenteilen (Früchte, Blüten, Laubwerk, Stengel, Knollen, Wurzeln) von unterschiedlichen Nutzkulturen die auftretenden Mikroorganismen eingedämmt oder vernichtet werden, wobei auch später zuwachsende Pflanzenteile von derartigen Mikroorganismen verschont bleiben. Dies trifft insbesondere auch auf Mikroorganismen zu, die gegen Fungizide aus der Triazol-Klasse reduzierte Sensitivität entwickelt haben.The active compound mixtures I + II according to the invention have very advantageous curative, preventive and systemic fungicidal properties for protecting crop plants. The present active ingredient mixtures on plants or on parts of plants (fruits, flowers, foliage, stems, tubers, roots) of different useful cultures can be used to contain or destroy the microorganisms which occur, with plant parts which are growing later being spared by such microorganisms. This applies in particular to microorganisms that have developed reduced sensitivity to fungicides from the triazole class.

Die Wirkstoff-Gemische sind gegen die den folgenden Klassen angehörenden phytopathogenen Pilze wirksam : Ascomyceten (z. B. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula) ; Basidiomyceten (z. B. die Gattungen Hemileia, Rhizoctonia, Puccinia) ; Fungi imperfecti (z. B. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Altemaria und insbesondere Pyricularia). Die Wirkstoffgemische wirken systemisch. Sie können auch als Beizmittel zur Behandlung von Saatgut (Früchte, Knollen, Kömer) und Pflanzenstecklingen zum Schutz vor Pilzinfektionen sowie gegen im Erdboden auftretende phytopathogene Pilze eingesetzt werden. Die erfindungsgemässen Wirkstoff-Gemische zeichnen sich durch besonders gute Pflanzenverträglichkeit und durch ihre Umweltfreundlichkeit aus.The active substance mixtures are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidiomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria, Cercospora, Altemaria and especially Pyricularia). The active ingredient mixtures have a systemic effect. They can also be used as dressing agents for the treatment of seeds (fruits, tubers, grains) and plant cuttings to protect against fungal infections and against phytopathogenic fungi occurring in the soil. The active substance mixtures according to the invention are notable for particularly good plant tolerance and for their environmental friendliness.

Als Zielkulturen für die hierin offenbarten Indikationsgebiete gelten im Rahmen dieser Erfindung z. B. folgende Pflanzenarten : Getreide : (Weizen, Gerste, Roggen, Hafer, Reis, Sorghum und Verwandte) ; Rüben : (Zucker- und Futterrüben) ; Kern-, Stein- und Beerenobst: (Aepfel, Birnen, Pflaumen, Pfirsiche, Mandeln, Kirschen, Erd-, Hirn- und Brombeeren) ; Hülsenfrüchte : (Bohnen, Linsen, Erbsen, Soja) ; Oelkulturen : (Raps, Senf, Mohn, Oliven, Sonnenblumen, Kokos, Rizinus, Kakao, Erdnüsse) ; Gurkengewächse : (Kürbis, Gurken, Melonen) ; Fasergewächse : (Baumwolle, Flachs, Hanf, Jute) ; Citrusfrüchte : (Orangen, Zitronen, Grapefruit, Mandarinen) ; Gemüsesorten : (Spinat, Kopfsalat, Spargel, Kohlarten, Möhren, Zwiebeln, Tomaten, Kartoffeln, Paprika); Lorbeergewächse : (Avocado, Cinnamonum, Kampfer) oder Pflanzen wie Mais, Tabak, Nüsse, Kaffee, Zuckerrohr, Tee, Weinreben, Hopfen, Bananen- und Naturkautschukgewächse sowie Zierpflanzen (Blumen, Sträucher, Laubbäume und Nadelbäume wie Koniferen). Diese Aufzählung stellt keine Limitierung dar.Target cultures for the areas of indication disclosed herein include z. B. the following types of plants: cereals: (wheat, barley, rye, oats, rice, sorghum and relatives); Beets: (sugar and fodder beets); Pome, stone and berry fruit: (apples, pears, plums, peaches, almonds, cherries, strawberries, strawberries and blackberries); Legumes: (beans, lentils, peas, soy); Oil cultures: (rapeseed, mustard, poppy seeds, olives, sunflowers, coconut, castor bean, cocoa, peanuts); Cucumber Family: (Pumpkin, Cucumber, Melon); Fiber plants: (cotton, flax, hemp, jute); Citrus fruits: (oranges, lemons, grapefruit, mandarins); Vegetables: (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel plants: (avocado, cinnamonum, camphor) or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, grapevines, hops, banana and natural rubber plants and ornamental plants (flowers, shrubs, deciduous trees and conifers such as conifers). This list is not a limitation.

Die Wirkstoff-Gemische der Formeln I und 11 werden üblicherweise in Form von Zusammensetzungen verwendet. Die Wirkstoffe der Formel I und die der Formel II können gleichzeitig, auf die zubehandelnde Fläche oder Pflanze gegeben werden, zusammen mit gegebenenfalls weiteren in der Formulierungstechnik üblichen Trägerstoffen, Tensiden oder anderen applikationsfördernden Zusätzen.The active ingredient mixtures of the formulas I and 11 are usually used in the form of compositions. The active ingredients of the formula I and those of the formula II can be applied simultaneously to the area or plant to be treated, together with any other carriers, surfactants or other application-promoting additives customary in formulation technology.

Geeignete Träger und Zusätze können fest oder flüssig sein und entsprechen den in der Formulierungstechnik zweckdienlichen Stoffen, wie z. B. natürlichen oder regenerierten mineralischen Stoffen, Lösungs-, Dispergier-, Netz-, Haft-, Verdickungs-, Binde- oder Düngemitteln.Suitable carriers and additives can be solid or liquid and correspond to the substances useful in formulation technology, such as. B. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

Ein bevorzugtes Verfahren zum Aufbringen eines Wirkstoff-Gemisches das mindestens je einen dieser Wirkstoffe I und 11 enthält, ist das Aufbringen auf die oberirdischen Pflanzenteile, vor allem das Blattwerk (Blattapplikation). Anzahl der Applikationen und Aufwandmenge richten sich nach den biologischen und klimatischen Lebensbedingungen für den Erreger. Die Wirkstoffe können aber auch über den Erdboden durch das Wurzelwerk in die Pflanze gelangen (systemische Wirkung), indem man den Standort der Pflanze mit einer flüssigen Zubereitung tränkt oder die Substanzen in fester Form in den Boden einbringt z. B. in Form von Granulat (Bodenapplikation). Die Verbindungen der Formeln I und II können auch auf Samenkörner aufgebracht werden (Coating), indem man die Körner entweder nacheinander in einer flüssigen Zubereitung eines Wirkstoffs tränkt oder sie mit einer bereits kombinierten Zubereitung beschichtet. Darüberhinaus sind in besonderen Fällen weitere Applikationsarten bei Pflanzen möglich, z. B. die gezielte Behandlung der Knospen oder der Fruchtstände.A preferred method of applying a mixture of active ingredients which contains at least one of each of these active ingredients I and 11 is the application to the aerial parts of the plants, in particular the foliage (leaf application). The number of applications and the application rate depend on the biological and climatic living conditions for the pathogen. The active ingredients can also get into the plant through the roots through the roots (systemic effect) by soaking the location of the plant with a liquid preparation or introducing the substances in solid form into the soil, e.g. B. in the form of granules (floor application). The compounds of the formulas I and II can also be applied to seeds (coating) by either soaking the grains in succession in a liquid preparation of an active ingredient or coating them with an already combined preparation. In addition, other types of application to plants are possible in special cases, e.g. B. the targeted treatment of the buds or the fruit heads.

Die Verbindungen der Kombination werden dabei in unveränderter Form oder vorzugsweise zusammen mit den in der Formulierungstechnik üblichen Hilfsmitteln eingesetzt und werden daher z. B. zu Emulsionskonzentraten, streichfähigen Pasten, direkt versprühbaren oder verdünnbaren Lösungen, verdünnten Emulsionen, Spritzpulvern, löslichen Pulvern, Stäubemitteln, Granulaten, durch Verkapselungen in z. B. polymeren Stoffen in bekannter Weise verarbeitet. Die Anwendungsverfahren wie Versprühen, Vernebeln, Verstäuben, Verstreuen, Bestreichen oder Giessen werden gleich wie die Art der Mittel den angestrebten Zielen und den gegebenen Verhältnissen entsprechend gewählt. Günstige Aufwandmengen liegen im allgemeinen bei 50 g bis 2 kg AS/ha, insbesondere bei 100 g bis 600 g AS/ha.The compounds of the combination are used in unchanged form or preferably together with the auxiliaries customary in formulation technology and are therefore used, for. B. to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation in z. B. polymeric materials processed in a known manner. The application methods, such as spraying, atomizing, dusting, scattering, brushing or pouring, are selected in the same way as the type of agent, in accordance with the intended objectives and the prevailing conditions. Favorable application rates are generally 50 g to 2 kg ai / ha, in particular 100 g to 600 g ai / ha.

Die Formulierungen werden in bekannter Weise hergestellt, z. B. durch inniges Vermischen und/oder Vermahlen der Wirkstoffe mit Streckmitteln, wie z. B. mit Lösungsmitteln, festen Trägerstoffen, und gegebenfalls oberflächenaktiven Verbindungen (Tensiden).The formulations are prepared in a known manner, e.g. B. by intimately mixing and / or grinding the active ingredients with extenders, such as. B. with solvents, solid carriers, and optionally surface-active compounds (surfactants).

Als Lösungsmittel können in Frage kommen : Aromatische Kohlenwasserstoffe, bevorzugt die Fraktionen C8 bis C,2, wie z. B. Xylolgemische oder substituierte Naphthaline, Phthalsäureester wie Dibutyl- oder Dioctylphthalat, aliphatische Kohlenwasserstoffe wie Cyclohexan oder Paraffine, Alkohole und Glykole sowie deren Ether und Ester, wie Ethanol, Ethylenglykol, Ethylenglykolmonomethyl- oder -ethylether, Ketone wie Cyclohexanon, stark polare Lösungsmittel wie N-Methyl-pyrrolidon, Dimethylsulfoxid oder Dimethylformamid, sowie gegebenenfalls epoxydierte Pflanzenöle wie epoxydiertes Kokosnussöl oder Sojaöl ; oder Wasser.Possible solvents are: Aromatic hydrocarbons, preferably fractions C 8 to C, 2 , such as. B. xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N -Methyl-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

Als feste Trägerstoffe, z. B. für Stäubemittel und dispergierbare Pulver, werden in der Regel natürliche Gesteinsmehle verwendet, wie Calcit, Talkum, Kaolin, Montmorillonit oder Attapulgit. Zur Verbesserung der physikalischen Eigenschaften können auch hochdisperse Kieselsäure oder hochdisperse saugfähige Polymerisate zugesetzt werden. Als gekörnte, adsorptive Granulatträger kommen poröse Typen wie z. B. Bimsstein, Ziegelbruch, Sepiolit oder Bentonit, als nicht sorptive Trägermaterialien z. B. Calcit oder Sand in Frage. Darüberhinaus kann eine Vielzahl von vorgranulierten Materialien anorganischer oder organischer Natur wie insbesondere Dolomit oder zerkleinerte Pflanzenrückstände verwendet werden. Besonders vorteilhafte, applikationsfördemde Zuschlagstoffe, die zu einer Reduktion der Aufwandmenge führen können, sind ferner natürliche (tierische oder pflanzliche) oder synthetische Phospholipide aus der Reihe der Kephaline und Lecithine, wie z. B. Phosphatidylethanolamin, Phosphatidylserin, Phosphatidylglycerin, Lysolecithin, Plasmalogene oder Cardiolipin, die man beispielsweise aus tierischen oder pflanzlichen Zellen, insbesondere aus Hirn, Herz, Leber, Eidotter oder Sojabohnen gewinnen kann. Verwendbare Handelsmischungen sind z. B. Phosphatidylchlorin-Mischungen. Synthetische Phospholipide sind z. B. Dioctanoylphosphatidylcholin und Dipalmitoylphosphatidylcholin.As solid carriers, e.g. B. for dusts and dispersible powders, natural rock flours are usually used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, highly disperse silica or highly disperse absorbent polymers can also be added. As granular, adsorptive granulate carriers come porous types such. As pumice, broken brick, sepiolite or bentonite, as non-sorptive support materials such. B. calcite or sand in question. In addition, a large number of pregranulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues can be used. Particularly advantageous, application-promoting additives that can lead to a reduction in the application rate are also natural (animal or vegetable) or synthetic phospholipids from the series of kephalins and lecithins, such as. B. phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol, lysolecithin, plasmalogens or cardiolipin, which can be obtained, for example, from animal or plant cells, in particular from the brain, heart, liver, egg yolk or soybeans. Usable commercial mixtures are e.g. B. phosphatidylchlorine mixtures. Synthetic phospholipids are e.g. B. dioctanoylphosphatidylcholine and dipalmitoylphosphatidylcholine.

Als oberflächenaktive Verbindungen kommen je nach Art der zu formulierenden Wirkstoffe der Formel I und 11 nichtionogene, kation- und/oder anionaktive Tenside mit guten Emulgier-, Dispergier- und Netzeigenschaften in Betracht. Unter Tensiden sind auch Tensidgemische zu verstehen.Depending on the nature of the active ingredients of the formula I and 11 to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as mixtures of surfactants.

Im folgenden bedeutet « Wirkstoff » ein Gemisch aus I und II im Verhältnis 1 :2 bis 1 :4. (% = Gewichtsprozent).

Figure imgb0003
In the following, “active ingredient” means a mixture of I and II in a ratio of 1: 2 to 1: 4. (% = Weight percent).
Figure imgb0003

Der Wirkstoff wird mit den Zusatzstoffen gut vermischt und in einer geeigneten Mühle gut vermahlen. Man erhält Spritzpulver, die sich mit Wasser zu Suspensionen jeder gewünschten Konzentration verdünnen lassen.

Figure imgb0004
The active ingredient is mixed well with the additives and ground well in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
Figure imgb0004

Aus diesem Konzentrat können durch Verdünnen mit Wasser Emulsionen jeder gewünschten Konzentration hergestellt werden.

Figure imgb0005
Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
Figure imgb0005

Man erhält anwendungsfertige Stäubemittel, indem der Wirkstoff mit dem Träger vermischt und auf einer geeigneten Mühle vermahlen wird.

Figure imgb0006
Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.
Figure imgb0006

Der Wirkstoff wird mit den Zusatzstoffen vermischt, vermahlen und mit Wasser angefeuchtet. Dieses Gemisch wird extrudiert und anschliessend im Luftstrom getrocknet.

Figure imgb0007
The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
Figure imgb0007

Der fein gemahlene Wirkstoff wird in einem Mischer auf das mit Polyethylenglykol angefeuchtete Kaolin gleichmässig aufgetragen. Auf diese Weise erhält man staubfreie Umhüllungs-Granulate.The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

Ein synergistischer Effekt liegt bei Fungiziden immer dann vor, wenn die fungizide Wirkung der Wirkstoffkombination grösser ist als die Summe aus der Wirkung der einzeln applizierten Wirkstoffe.Fungicides always have a synergistic effect if the fungicidal activity of the active ingredient combination is greater than the sum of the effects of the individually applied active ingredients.

Die zu erwartende Wirkung E für eine gegebene Wirkstoff-Kombination, z. B. zweier Fungizide, gehorcht der sogenannten COLBY-Formel [ursprünglich nur zur Berechnung des Erwartungswertes E von Herbizidmischungen verwendet] :

Figure imgb0008
wobei X = % Wirkung durch Fungizid 1 bei p g AS/ha,

  • Y = % Wirkung durch Fungizid II bei q g AS/ha
  • E = Erwartete Wirkung der Fungizide I + II bei p + q g Aktivsubstanz per Hektar.
    • [1) COLBY, LR. « Calculating synergistic and antagonistic responses of herbicide combination ». Weeds 15, S. 20-22.
    • 2) LIMPEL and al., 1062 « Weeds control by ... certain combinations ». Proc. NEWCL. Vol. 16, S. 48-53]
The expected effect E for a given combination of active ingredients, e.g. B. two fungicides, obeys the so-called COLBY formula [originally only used to calculate the expected value E of herbicide mixtures]:
Figure imgb0008
 where X =% effect by fungicide 1 at pg AS / ha,
  • Y =% effect by fungicide II at qg AS / ha
  • E = expected effect of fungicides I + II with p + qg active substance per hectare.
    • [1) COLBY, LR. "Calculating synergistic and antagonistic responses of herbicide combination". Weeds 15, pp. 20-22.
    • 2) LIMPEL and al., 1062 "Weeds control by ... certain combinations". Proc. NEWCL. Vol. 16, pp. 48-53]

Wenn die tatsächlich beobachtete Wirkung (O) grösser ist als die berechnete (E), so ist die Kombination in ihrer Wirkung überadditiv, d. h. es liegt ein synergistischer Effekt vor.If the actually observed effect (O) is greater than the calculated (E), the combination of the combination is superadditive, i.e. H. there is a synergistic effect.

In den nachfolgenden Beispielen wurde E gemäss obiger Gleichung berechnet.

Figure imgb0009
In the examples below, E was calculated according to the equation above.
Figure imgb0009

In 11 cm tiefen Saatschalen (Fläche 30 x 40 cm) werden im Gewächshaus bei 20 °C ca. 95 Pflanzen der Winterweizensorte « Kanzler herangezogen. Im 2-Blatt-Stadium werden die Pflanzen mit einem Isolat von Erysiphe graminis tritici inokuliert, das eine reduzierte Sensitivität gegen DMI-Fungizide aufweist.In 11 cm deep seed bowls (area 30 x 40 cm), approx. 95 plants of the winter wheat variety «Chancellor» are grown in the greenhouse at 20 ° C. In the 2-leaf stage, the plants are inoculated with an isolate of Erysiphe graminis tritici, which has a reduced sensitivity to DMI fungicides.

Bei Sichtbarwerden des Befalls 5 Tage nach Inokulation (3-Blatt-Stadium ; Befall 10-12 %) wird der Einzelwirkstoff bzw. das Fungizid-Gemisch als wässrige Suspension mit einem Spritzbalken unter Feldbedingungen appliziert. Nach der Applikation wird die Veränderung des Befalls auf der bei Inokulation vorhandenen Blattfläche (Auswertung des Primärbefalls) in regelmässigen Abständen bestimmt.If the infestation becomes visible 5 days after inoculation (3-leaf stage; infestation 10-12%), the individual active ingredient or the fungicide mixture is applied as an aqueous suspension with a spray bar under field conditions. After the application, the change in the infestation on the leaf surface present in the case of inoculation (evaluation of the primary infestation) is determined at regular intervals.

Es werden die in der Tabelle wiedergegebenen Aufwandmengen eingesetzt. Jeder der 16 Teil-Versuche läuft in 3 Wiederholungen.

Figure imgb0010
The application rates shown in the table are used. Each of the 16 part attempts runs in 3 repetitions.
Figure imgb0010

Wie ersichtlich, tritt bei ganz unterschiedlichen Mischungsverhältnissen in den Versuchen Nr. 9 bis Nr. 16 eine synergistisch gesteigerte Fungizid-Wirkung auf.As can be seen, tests 9 to 16 have a synergistically increased fungicidal action with very different mixing ratios.

Aehnliche synergistisch gesteigerte Wirkungen werden auch gegen Gerstenmehltau, Getreiderost-Arten (Puccinia spp.) und andere Pathogene erzielt.Similar synergistically increased effects are also achieved against barley mildew, cereal rust species (Puccinia spp.) And other pathogens.

Claims (10)

1. A composition for controlling phytopathogenic fungi and for preventing fungus attack based on a mixture of two plant fungicides in admixture with a suitable carrier and/or extender, wherein the composition contains as component I the active ingredient 1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-ylmethyl]-1 H-1,2,4-triazole ( = propiconazol) of formula I
Figure imgb0015
or a salt thereof and as component II the active ingredient 4-[3-(4-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine ( = fenpropimorph) of formula II
Figure imgb0016
or a salt thereof in an amount producing synergistic fungicidal activity.
2. A composition according to claim 1, wherein propiconazol is mainly in the form of the two cis-enantiomers.
3. A composition according to claim 2, wherein propiconazol is mainly in the form of one of the cis-enantiomers and fenpropimorph is mainly in the form of the (-) cis-enantiomer.
4. A composition according to claim 1, wherein the weight ratio of I : II is 10 : 1 to 1 : 20.
5. A composition according to claim 4, wherein the weight ratio of I : II is 5 1 to 1 : 5.
6. A composition according to claim 5, wherein the weight ratio of I : II is 1 : 1 to 1 : 5.
7. Use of an active component combination according to claim 1 for controlling fungi or for preventing fungus attack.
8. A method of controlling fungi, which method comprises treating a locus which is already infected by fungi, or is liable to be infected, simultaneously, with a) the active component propiconazol of formula I
Figure imgb0017
or a salt thereof and with b) the active component fenpropimorph of formula II
Figure imgb0018
or a salt thereof.
9. A method according to claim 8, which comprises the use of propiconazol mainly in the form of the two cis-enantiomers.
10. A method according to claim 9, which comprises the use of propiconazol mainly in the form of one of the cis-enantiomers and of fenpropimorph mainly in the form of the (-) cis-enantiomer.
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ATE44852T1 (en) * 1986-02-14 1989-08-15 Ciba Geigy Ag MICROBICIDES.
US4940799A (en) * 1987-07-20 1990-07-10 Ciba-Geigy Corporation Preparation of the diastereomeric mixture 2R,4S-1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylmethyl]-1H-1,2,4-triazole
EP0370951B1 (en) * 1988-11-18 1993-08-11 Ciba-Geigy Ag Microbicidal agents
DE3902509A1 (en) * 1989-01-28 1990-08-09 Basf Ag FUNGICIDAL MIXTURE
FR2655514A1 (en) * 1989-12-13 1991-06-14 Rhone Poulenc Agrochimie FUNGICIDE ASSOCIATION WITH SYNERGISTIC EFFECT BASED ON MORPHOLINE AND TRIAZOLE.
DE59107460D1 (en) * 1990-11-02 1996-04-04 Ciba Geigy Ag Fungicidal agents
CH680895A5 (en) * 1990-11-02 1992-12-15 Ciba Geigy Ag
US5330984A (en) * 1990-11-02 1994-07-19 Ciba-Geigy Corporation Fungicidal compositions
EP0898506A1 (en) * 1996-04-19 1999-03-03 Dr. Wolman GmbH Process for treating wood against infection by moulds harmful to wood
EP2368433B1 (en) * 2010-03-24 2014-05-07 Cognis IP Management GmbH Biocide compositions comprising glycerol(ether)phosphates
CN102225935B (en) * 2011-04-27 2014-04-02 山东潍坊双星农药有限公司 Manufacturing method of proPiconazole

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ179111A (en) * 1974-11-18 1978-03-06 Janssen Pharmaceutica Nv I-(aryl)-ethyl-1h-1,2,4-triazole ketals,anti-microbial and plant growth controlling compositions
US4079062A (en) * 1974-11-18 1978-03-14 Janssen Pharmaceutica N.V. Triazole derivatives
JPS5246075A (en) * 1975-10-09 1977-04-12 Janssen Pharmaceutica Nv 11*betaaaryl* ethyll1hh 1*2*44triazolketal and pharmaceutically acceptable acid adduct salt thereof
AT354187B (en) * 1976-11-22 1979-12-27 Hoffmann La Roche FUNGICIDE AGENT
US4434165A (en) * 1980-09-30 1984-02-28 Hoffmann-La Roche Inc. Fungicidal compositions
EP0095242A3 (en) * 1982-05-17 1985-12-27 Imperial Chemical Industries Plc Fungicidal compositions and methods of treating seeds and combating fungal pest therewith
NL8402979A (en) * 1984-09-28 1986-04-16 Tno METHOD FOR CONTROLLING VEGASOLIC DISEASES IN CROPS, ESPECIALLY DISEASE.
DE3605551A1 (en) * 1986-02-21 1987-09-10 Bayer Ag FUNGICIDAL AGENT

Also Published As

Publication number Publication date
ZA871582B (en) 1988-04-27
JPH0432041B2 (en) 1992-05-28
FI870959A0 (en) 1987-03-04
DE3760318D1 (en) 1989-08-24
IL81770A (en) 1991-04-15
NO870930L (en) 1987-09-07
GR3000105T3 (en) 1990-11-29
PT84396A (en) 1987-04-01
HUT43236A (en) 1987-10-28
DD257575A5 (en) 1988-06-22
GR890300075T1 (en) 1989-09-29
AU601717B2 (en) 1990-09-20
PL264441A1 (en) 1988-07-21
ES2009855B3 (en) 1989-10-16
US4925842A (en) 1990-05-15
DK164888C (en) 1993-01-18
DK164888B (en) 1992-09-07
ATE44641T1 (en) 1989-08-15
FI88665C (en) 1993-06-28
SU1655292A3 (en) 1991-06-07
JPS62212307A (en) 1987-09-18
DK113687D0 (en) 1987-03-05
DK113687A (en) 1987-09-07
NO870930D0 (en) 1987-03-05
CA1273291A (en) 1990-08-28
HU204170B (en) 1991-12-30
PT84396B (en) 1989-10-04
EP0237483A1 (en) 1987-09-16
IE59418B1 (en) 1994-02-23
AU6973587A (en) 1987-09-10
FI88665B (en) 1993-03-15
CS141487A2 (en) 1988-11-15
BR8701014A (en) 1987-12-29
CS264347B2 (en) 1989-07-12
BG46593A3 (en) 1990-01-15
NO169471C (en) 1992-07-01
IE870564L (en) 1987-09-06
NO169471B (en) 1992-03-23
FI870959A (en) 1987-09-07
PL149880B1 (en) 1990-03-31

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